The ChIP reaction basis set, 2026

Operators added since the original basis · 06 August 2026

The basis has grown from 75 operators to 86, and the curated feedstock behind them from 3,818,459 to 4,736,345 entries. The eleven additions are below, each drawn firing on real members of its own pools rather than shown as a SMARTS string.

The selection is deliberate rather than opportunistic. Nine of the eleven are bond constructions that became routine in kinase medicinal chemistry after the original work, and their absence meant whole regions of accessible chemistry could not be reached: no biaryl coupling, no triazole, no sulfonamide, no aryl amination. The tenth builds a heteroaromatic core in place rather than requiring it as a purchased fragment, and the eleventh is not a reaction at all.

BasisOperatorsFeedstock entries
Original753,818,459
2026864,736,345

The eleven additions

r9000 Catalogue passthrough 826,023 building blocks

Not a reaction. Admits any catalogue compound into a route unchanged, so a protocol can begin from a purchasable molecule rather than requiring a bond-forming first step. Its pool is the whole feedstock, which is why it is by far the largest.

one of 826,023 catalogue compounds, admitted unchanged
reaction SMARTS[A,a:1]>>[A,a:1]
r9210 Sulfonamide formation 5,000 × 5,000 building blocks

Amine plus sulfonyl chloride. One of the most heavily used bond constructions in kinase medicinal chemistry and absent from the original basis.

reaction SMARTS[N;!H0:1][H].[S;$(S(=O)(=O)(Cl)[A,a]):2](=[O:3])(=[O:4])(Cl)[A,a:5]>>[N:1][S:2](=[O:3])(=[O:4])[A,a:5]
r9211 Reductive amination 5,000 × 5,000 building blocks

Amine plus aldehyde to the secondary amine. The standard way to install a basic nitrogen with control over substitution.

reaction SMARTS[N;!H0:1][H].[C;$([C;!H0](=O)[A,a]):2](=[O:3])([A,a:4])[H]>>[N:1][C;!H0:2]([A,a:4])([H])[H]
r9212 Sonogashira coupling 5,000 × 5,000 building blocks

Aryl halide plus terminal alkyne. Introduces rigid linear linkers, which the 2005 basis had no route to.

reaction SMARTS[c:1][Br,I].[C;!H0:2]([H])#[C:3][A,a:4]>>[c:1][C:2]#[C:3][A,a:4]
r9213 Azide-alkyne cycloaddition (CuAAC) 5,000 × 4,266 building blocks

Terminal alkyne plus organic azide to the 1,4-triazole. Post-dates the original basis entirely and is now ubiquitous.

reaction SMARTS[C;!H0:1]#[C:2][A,a:3].[A,a:7][N:4]=[N+:5]=[N-:6]>>[n+0:4]1([A,a:7])[c:1][c:2]([A,a:3])[n+0:6][n+0:5]1
r9214 Esterification 5,000 × 5,000 building blocks

Carboxylic acid plus alcohol.

reaction SMARTS[C;$(C(=O)[OH]):1](=[O:2])[OH].[O;!H0:3]([H])[C;!H0:4]>>[C:1](=[O:2])[O:3][C:4]
r9215 Pyrazole formation 4,854 × 1,577 building blocks

Hydrazine plus 1,3-dicarbonyl. Builds the heteroaromatic core in one step rather than requiring it as a purchased fragment.

reaction SMARTS[A,a:8][N;!H0:1]([H])[N;!H0;!H1:2]([H])[H].[C;$(C(=O)[C;!H0;!H1]C=O):3](=O)[C;!H0;!H1:4]([H])[C;$(C(=O)):5]=O>>[n:1]1([A,a:8])[c:3][c:4][c:5][n:2]1
r9216 Suzuki-Miyaura coupling 5,000 × 1,166 building blocks

Aryl halide plus arylboronic acid to the biaryl. The single most used C-C bond formation in the modern kinase literature.

reaction SMARTS[c:1][Br,I].[c:2]B([OH])[OH]>>[c:1][c:2]
r9217 Aryl amination 5,000 × 5,000 building blocks

Aryl halide plus amine (Buchwald-Hartwig conditions).

reaction SMARTS[c:1][Br,I].[N;!H0:2][H]>>[c:1][N:2]
r9218 Heteroaryl SNAr 5,000 × 5,000 building blocks

Chloro-azine plus amine. The classic hinge-binder attachment in kinase inhibitors, exploiting activation by the ring nitrogen.

reaction SMARTS[c;$(c[n]):1][Cl].[N;!H0:2][H]>>[c:1][N:2]
r9219 Williamson ether synthesis 5,000 × 5,000 building blocks

Alcohol plus alkyl halide.

reaction SMARTS[O;!H0:1]([H])[A,a:2].[C;!H0;$([C;!H0][Br,I,Cl]):3][Br,I,Cl]>>[A,a:2][O:1][C:3]

Validation

Every operator is checked before use: that it fires on its own pools, that each reactant slot has feedstock, that no pool is empty, that no catalogue identifier is fabricated or blank, that the legacy operators load identical pools under the new basis, and that each new operator appears in the successor-compatibility map and is not isolated within it. The full suite is twelve checks and all must pass before a run starts.

Reaction schemes are generated by applying each operator to randomly drawn members of its own curated pools. Structures are therefore real feedstock, and the products are what the operator actually produces.
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